(Diethyl­enetri­amine-N,N',N'')(DL-histinato-N,N',O)nickel(II) iodide monohydrate

The asymmetric unit of the title compound, [Ni(C₄H₁₃N₃)(C₆H₈N₃O₂)]I·H₂O, comprises a six-coordinated Ni(II) complex cation, an I^- anion, and one water molecule of crystallization. Intermolecular hydrogen bonds link the complex cations into extended two-dimensional layers.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.004 Å
• R factor = 0.022
• wR factor = 0.051
• Data-to-parameter ratio = 19.1

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry


 Alert Level C:



ABSTM_02  Alert C The ratio of expected to reported Tmax/Tmin(RR) is > 1.10
          Tmin and Tmax reported:      0.322     0.483
          Tmin and Tmax expected:      0.249     0.427
          RR =      1.142
          Please check that your absorption correction is appropriate.

PLAT_420  Alert C D-H Without Acceptor       N2     -   H2D               ?

PLAT_420  Alert C D-H Without Acceptor       N3     -   H3C               ?

General Notes



ABSTM_02  When printed, the submitted absorption T values will be replaced
          by the scaled T values. Since the ratio of scaled T's is
          identical to the ratio of reported T values, the scaling does
          not imply a change to the absorption corrections used in the
          study.
          Ratio of Tmax expected/reported      0.884
          Tmax scaled      0.427 Tmin scaled      0.284


 0 Alert Level A = Potentially serious problem

 0 Alert Level B = Potential problem

 3 Alert Level C = Please check

---

S1. Comment

Previously we have reported the crystal structures of a series of amino acidato complexes with the formula [M(N4)(amino acidato)]ⁿ⁺, where N4 = triethylenetetraamine (trien) or tris(2-aminoethyl)amine (tren), M = Co³⁺, n = 2+ and M = Ni²⁺, n = 1+ (Cai et al., 2000, 2001, 2002; Hu et al., 2001). Their interesting packing arrangements directed by intermolecular hydrogen bonds were also discussed. Compared with the cobalt(III) analogues, structures of Ni(II) amino acidato complexes are less well documented (Cai et al., 2002).

In the title compound, Ni(II) is six-coordinated by three nitrogen atoms of the diethylenetriamine (dien) ligand, two N atoms and one O atom of the histidine ligand, as shown in Fig.1. Histidine is a potential multidentate ligand displaying varying coordination modes in different chemical environments. In the reported compond [Co(trien)(histidinato)](ClO₄)₂·2H₂O (Hu et al., 2001), histidine is coordinated to Co(III) through one of the imidazol nitrogen atoms and the amino N atom. There are only two structures in the Cambridge Structural Database (Allen & Kennard, 1993) showing the tridentate coordination mode of histidine with Ni(II), namely [Ni(histidinato)(SCN)(H₂O)₂]·H₂O (Shvelashvili et al., 1980, 1984; Sakurai et al., 1978) and [Ni(histidinato)₂]·H₂O (Shvelashvili et al., 1984; Sakurai et al., 1978). The bond lengths and angles of the Ni(II) coordination geometry in (I) are in agreement with these structures. The C–O bond lengths of the carboxylate group are 1.269 (3) and 1.235 (3) Å respectively, indicative of conjugated bonds.

As shown in Fig.2, the catonic complex is connected to another one, related by an inversion center, through complementary hydrogen bonds, formed by the free carboxylate oxygen atoms and the amino hydrogen atoms of both the dien and histidine ligands, leading to racemic pairs. These racemic pairs are further linked to each other via hydrogen bonds formed by the free carboxylate oxygen and the imidazol amino hydrogen and form an extended two-dimensional network along the bc plane. Both the crystalline water molecule and I^- are involved in extensive hydrogen bonding with the cation, as shown in Table 1.

S2. Experimental

I was obtained by the method described elsewhere (Cai et al., 2002).

S3. Refinement

All hydrogen atoms of the ligands were placed in idealized positions and refined as riding atoms with with fixed individual displacement parameters [U(H) = 1.2 U_eq(N), U(H) = 1.2 U_eq(C)]. Hydrogen atoms of the water molecules were located from the difference Fourier map. Their coordinates were not refined but their displacement parameters.

Computing details

Data collection: SMART (Bruker, 1998); cell refinement: SMART; data reduction: SAINT-Plus (Bruker, 1999); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1998 ); software used to prepare material for publication: SHELXTL.

Figures

	Fig. 1. Contents of the asymmetric unit showing 30% probability displacement ellipsoids.
	Fig. 2. Packing arrangement of the cations. Iodide, water of hydration and hydrogen atoms attached to carbons are omitted for clarity.

(diethylenetriamine-N,N',N'')(DL-histinato-N,N',O)nickel(II) iodide monohydrate

Crystal data

[Ni(C4H13N3)(C6H8N3O2)]I·H2O	F(000) = 920
Mr = 460.95	Dx = 1.775 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
a = 9.384 (5) Å	Cell parameters from 813 reflections
b = 15.323 (7) Å	θ = 2.9–25.3°
c = 12.667 (6) Å	µ = 2.93 mm^−1
β = 108.758 (8)°	T = 293 K
V = 1724.6 (14) Å^3	Block, purple
Z = 4	0.50 × 0.41 × 0.29 mm

Data collection

CCD area detector diffractometer	3673 independent reflections
Radiation source: fine-focus sealed tube	3280 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.018
phi and ω scans	θmax = 27.0°, θmin = 2.2°
Absorption correction: multi-scan (SADABS: Sheldrick, 1996; Blessing, 1995)	h = −11→7
Tmin = 0.322, Tmax = 0.483	k = −19→17
9823 measured reflections	l = −16→16

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.022	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.051	H atoms treated by a mixture of independent and constrained refinement
S = 1.08	w = 1/[σ^2(Fo^2) + (0.0191P)^2 + 1.0794P] where P = (Fo^2 + 2Fc^2)/3
3673 reflections	(Δ/σ)max = 0.002
192 parameters	Δρmax = 0.60 e Å^−3
0 restraints	Δρmin = −0.68 e Å^−3

Special details

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
I1	0.363034 (18)	0.103023 (10)	0.688563 (14)	0.04352 (6)
Ni1	0.79822 (3)	0.915238 (16)	0.75632 (2)	0.02584 (7)
N1	0.9742 (2)	0.98089 (12)	0.71850 (14)	0.0328 (4)
H1C	1.0181	1.0197	0.7738	0.039*
N2	0.6680 (2)	0.97424 (13)	0.60666 (15)	0.0380 (4)
H2C	0.6568	0.9379	0.5488	0.046*
H2D	0.5762	0.9882	0.6097	0.046*
N3	0.8878 (2)	0.80687 (12)	0.69617 (15)	0.0336 (4)
H3C	0.9263	0.7686	0.7520	0.040*
H3D	0.8140	0.7799	0.6425	0.040*
N4	0.7454 (2)	1.01534 (11)	0.85211 (14)	0.0306 (4)
H4C	0.8137	1.0586	0.8647	0.037*
H4D	0.6537	1.0375	0.8167	0.037*
N5	0.4510 (2)	0.74343 (13)	0.75751 (18)	0.0442 (5)
H5B	0.3929	0.6999	0.7305	0.053*
N6	0.6226 (2)	0.84410 (12)	0.77719 (15)	0.0337 (4)
C1	0.9110 (3)	1.02831 (16)	0.61223 (19)	0.0418 (5)
H1A	0.9166	0.9918	0.5512	0.050*
H1B	0.9698	1.0805	0.6132	0.050*
C2	0.7500 (3)	1.05306 (17)	0.5943 (2)	0.0459 (6)
H2A	0.7448	1.0966	0.6485	0.055*
H2B	0.7055	1.0775	0.5203	0.055*
C3	1.0063 (3)	0.83522 (16)	0.6509 (2)	0.0428 (5)
H3A	0.9622	0.8497	0.5726	0.051*
H3B	1.0780	0.7883	0.6574	0.051*
C4	1.0854 (3)	0.91398 (16)	0.7147 (2)	0.0424 (5)
H4A	1.1437	0.8970	0.7900	0.051*
H4B	1.1539	0.9378	0.6789	0.051*
C5	0.7486 (2)	0.97372 (13)	0.95797 (16)	0.0303 (4)
H5A	0.7617	1.0192	1.0147	0.036*
C6	0.8836 (2)	0.91176 (12)	0.99501 (17)	0.0293 (4)
C7	0.6011 (3)	0.92577 (16)	0.94445 (19)	0.0381 (5)
H7A	0.6054	0.9024	1.0166	0.046*
H7B	0.5201	0.9682	0.9235	0.046*
C8	0.5610 (2)	0.85304 (14)	0.86167 (18)	0.0326 (4)
C9	0.5533 (3)	0.77723 (15)	0.71655 (19)	0.0397 (5)
H9A	0.5731	0.7565	0.6537	0.048*
C10	0.4551 (3)	0.79035 (16)	0.8500 (2)	0.0439 (6)
H10A	0.3967	0.7811	0.8960	0.053*
O1	0.93527 (18)	0.88474 (10)	0.91983 (12)	0.0350 (3)
O2	0.9352 (2)	0.89227 (10)	1.09468 (12)	0.0395 (4)
O1W	0.1850 (2)	0.78154 (13)	0.99661 (15)	0.0572 (5)
HW1	0.0993	0.8123	0.9720	0.087 (12)*
HW2	0.1524	0.7352	0.9496	0.085 (12)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
I1	0.03620 (9)	0.04348 (10)	0.04843 (10)	0.00282 (6)	0.01021 (7)	−0.00072 (6)
Ni1	0.02600 (14)	0.02975 (13)	0.02187 (13)	−0.00023 (10)	0.00783 (10)	−0.00186 (9)
N1	0.0315 (9)	0.0380 (10)	0.0280 (9)	−0.0049 (8)	0.0084 (7)	−0.0035 (7)
N2	0.0326 (10)	0.0525 (12)	0.0260 (9)	0.0051 (9)	0.0056 (8)	0.0006 (8)
N3	0.0340 (10)	0.0349 (10)	0.0324 (9)	0.0008 (8)	0.0113 (8)	−0.0032 (7)
N4	0.0322 (9)	0.0282 (8)	0.0276 (9)	0.0038 (7)	0.0046 (7)	0.0007 (7)
N5	0.0399 (11)	0.0397 (11)	0.0529 (12)	−0.0138 (9)	0.0146 (10)	−0.0089 (9)
N6	0.0350 (10)	0.0339 (9)	0.0359 (10)	−0.0054 (8)	0.0167 (8)	−0.0082 (7)
C1	0.0495 (14)	0.0435 (13)	0.0353 (12)	−0.0054 (11)	0.0177 (11)	0.0057 (10)
C2	0.0555 (16)	0.0473 (14)	0.0346 (12)	0.0079 (12)	0.0141 (11)	0.0117 (10)
C3	0.0431 (14)	0.0470 (14)	0.0455 (13)	0.0049 (11)	0.0242 (11)	−0.0046 (11)
C4	0.0285 (12)	0.0525 (14)	0.0485 (14)	−0.0011 (10)	0.0156 (10)	−0.0015 (11)
C5	0.0366 (11)	0.0286 (10)	0.0248 (10)	0.0021 (8)	0.0089 (9)	−0.0058 (8)
C6	0.0345 (11)	0.0249 (10)	0.0264 (10)	−0.0023 (8)	0.0067 (9)	−0.0019 (7)
C7	0.0397 (13)	0.0446 (12)	0.0359 (12)	0.0025 (10)	0.0203 (10)	−0.0063 (10)
C8	0.0292 (11)	0.0370 (11)	0.0339 (11)	0.0013 (9)	0.0135 (9)	−0.0013 (9)
C9	0.0418 (13)	0.0386 (12)	0.0403 (12)	−0.0067 (10)	0.0156 (11)	−0.0099 (10)
C10	0.0391 (13)	0.0486 (14)	0.0497 (14)	−0.0061 (11)	0.0224 (11)	−0.0012 (11)
O1	0.0381 (8)	0.0399 (8)	0.0259 (7)	0.0117 (7)	0.0087 (6)	0.0024 (6)
O2	0.0531 (10)	0.0373 (8)	0.0240 (7)	0.0041 (7)	0.0067 (7)	0.0033 (6)
O1W	0.0542 (11)	0.0668 (13)	0.0436 (10)	0.0238 (10)	0.0060 (9)	0.0018 (9)

Geometric parameters (Å, º)

Ni1—N6	2.0621 (19)	C1—C2	1.503 (4)
Ni1—N2	2.1011 (19)	C1—H1A	0.9700
Ni1—O1	2.1092 (17)	C1—H1B	0.9700
Ni1—N4	2.1111 (18)	C2—H2A	0.9700
Ni1—N3	2.1111 (19)	C2—H2B	0.9700
Ni1—N1	2.1162 (19)	C3—C4	1.508 (3)
N1—C4	1.474 (3)	C3—H3A	0.9700
N1—C1	1.476 (3)	C3—H3B	0.9700
N1—H1C	0.9100	C4—H4A	0.9700
N2—C2	1.467 (3)	C4—H4B	0.9700
N2—H2C	0.9000	C5—C7	1.527 (3)
N2—H2D	0.9000	C5—C6	1.531 (3)
N3—C3	1.471 (3)	C5—H5A	0.9800
N3—H3C	0.9000	C6—O2	1.235 (3)
N3—H3D	0.9000	C6—O1	1.269 (3)
N4—C5	1.476 (3)	C7—C8	1.493 (3)
N4—H4C	0.9000	C7—H7A	0.9700
N4—H4D	0.9000	C7—H7B	0.9700
N5—C9	1.334 (3)	C8—C10	1.356 (3)
N5—C10	1.365 (3)	C9—H9A	0.9300
N5—H5B	0.8600	C10—H10A	0.9300
N6—C9	1.320 (3)	O1W—HW1	0.8967
N6—C8	1.377 (3)	O1W—HW2	0.9144
N6—Ni1—N2	94.94 (8)	N1—C1—H1B	109.5
N6—Ni1—O1	90.98 (7)	C2—C1—H1B	109.5
N2—Ni1—O1	167.26 (7)	H1A—C1—H1B	108.1
N6—Ni1—N4	88.03 (7)	N2—C2—C1	108.2 (2)
N2—Ni1—N4	91.72 (8)	N2—C2—H2A	110.1
O1—Ni1—N4	77.19 (7)	C1—C2—H2A	110.1
N6—Ni1—N3	93.31 (8)	N2—C2—H2B	110.1
N2—Ni1—N3	101.33 (8)	C1—C2—H2B	110.1
O1—Ni1—N3	89.56 (7)	H2A—C2—H2B	108.4
N4—Ni1—N3	166.71 (7)	N3—C3—C4	109.31 (18)
N6—Ni1—N1	173.81 (7)	N3—C3—H3A	109.8
N2—Ni1—N1	82.02 (8)	C4—C3—H3A	109.8
O1—Ni1—N1	93.09 (7)	N3—C3—H3B	109.8
N4—Ni1—N1	97.42 (8)	C4—C3—H3B	109.8
N3—Ni1—N1	82.06 (8)	H3A—C3—H3B	108.3
C4—N1—C1	113.19 (18)	N1—C4—C3	110.04 (19)
C4—N1—Ni1	106.77 (14)	N1—C4—H4A	109.7
C1—N1—Ni1	109.06 (14)	C3—C4—H4A	109.7
C4—N1—H1C	109.2	N1—C4—H4B	109.7
C1—N1—H1C	109.2	C3—C4—H4B	109.7
Ni1—N1—H1C	109.2	H4A—C4—H4B	108.2
C2—N2—Ni1	106.12 (14)	N4—C5—C7	110.67 (17)
C2—N2—H2C	110.5	N4—C5—C6	108.62 (16)
Ni1—N2—H2C	110.5	C7—C5—C6	111.52 (18)
C2—N2—H2D	110.5	N4—C5—H5A	108.7
Ni1—N2—H2D	110.5	C7—C5—H5A	108.7
H2C—N2—H2D	108.7	C6—C5—H5A	108.7
C3—N3—Ni1	110.30 (14)	O2—C6—O1	124.7 (2)
C3—N3—H3C	109.6	O2—C6—C5	118.49 (19)
Ni1—N3—H3C	109.6	O1—C6—C5	116.77 (17)
C3—N3—H3D	109.6	C8—C7—C5	116.89 (18)
Ni1—N3—H3D	109.6	C8—C7—H7A	108.1
H3C—N3—H3D	108.1	C5—C7—H7A	108.1
C5—N4—Ni1	105.55 (12)	C8—C7—H7B	108.1
C5—N4—H4C	110.6	C5—C7—H7B	108.1
Ni1—N4—H4C	110.6	H7A—C7—H7B	107.3
C5—N4—H4D	110.6	C10—C8—N6	108.74 (19)
Ni1—N4—H4D	110.6	C10—C8—C7	128.0 (2)
H4C—N4—H4D	108.8	N6—C8—C7	123.10 (19)
C9—N5—C10	107.7 (2)	N6—C9—N5	110.9 (2)
C9—N5—H5B	126.1	N6—C9—H9A	124.5
C10—N5—H5B	126.1	N5—C9—H9A	124.5
C9—N6—C8	106.13 (18)	C8—C10—N5	106.5 (2)
C9—N6—Ni1	126.91 (15)	C8—C10—H10A	126.8
C8—N6—Ni1	126.83 (14)	N5—C10—H10A	126.8
N1—C1—C2	110.61 (18)	C6—O1—Ni1	113.91 (14)
N1—C1—H1A	109.5	HW1—O1W—HW2	96.1
C2—C1—H1A	109.5
N2—Ni1—N1—C4	−123.43 (15)	Ni1—N2—C2—C1	49.1 (2)
O1—Ni1—N1—C4	68.40 (14)	N1—C1—C2—N2	−52.4 (3)
N4—Ni1—N1—C4	145.87 (14)	Ni1—N3—C3—C4	31.7 (2)
N3—Ni1—N1—C4	−20.73 (14)	C1—N1—C4—C3	−75.7 (2)
N2—Ni1—N1—C1	−0.79 (14)	Ni1—N1—C4—C3	44.3 (2)
O1—Ni1—N1—C1	−168.97 (14)	N3—C3—C4—N1	−51.5 (3)
N4—Ni1—N1—C1	−91.49 (15)	Ni1—N4—C5—C7	−81.26 (17)
N3—Ni1—N1—C1	101.91 (15)	Ni1—N4—C5—C6	41.48 (17)
N6—Ni1—N2—C2	158.90 (15)	N4—C5—C6—O2	157.18 (18)
O1—Ni1—N2—C2	41.5 (4)	C7—C5—C6—O2	−80.6 (2)
N4—Ni1—N2—C2	70.73 (15)	N4—C5—C6—O1	−22.2 (2)
N3—Ni1—N2—C2	−106.72 (15)	C7—C5—C6—O1	100.0 (2)
N1—Ni1—N2—C2	−26.53 (15)	N4—C5—C7—C8	61.2 (3)
N6—Ni1—N3—C3	169.71 (15)	C6—C5—C7—C8	−59.8 (3)
N2—Ni1—N3—C3	74.00 (16)	C9—N6—C8—C10	0.2 (3)
O1—Ni1—N3—C3	−99.34 (15)	Ni1—N6—C8—C10	−175.82 (16)
N4—Ni1—N3—C3	−94.8 (3)	C9—N6—C8—C7	−175.4 (2)
N1—Ni1—N3—C3	−6.16 (15)	Ni1—N6—C8—C7	8.5 (3)
N6—Ni1—N4—C5	55.03 (13)	C5—C7—C8—C10	165.6 (2)
N2—Ni1—N4—C5	149.92 (13)	C5—C7—C8—N6	−19.6 (3)
O1—Ni1—N4—C5	−36.42 (13)	C8—N6—C9—N5	0.2 (3)
N3—Ni1—N4—C5	−41.0 (4)	Ni1—N6—C9—N5	176.22 (16)
N1—Ni1—N4—C5	−127.91 (13)	C10—N5—C9—N6	−0.5 (3)
N2—Ni1—N6—C9	69.6 (2)	N6—C8—C10—N5	−0.5 (3)
O1—Ni1—N6—C9	−121.7 (2)	C7—C8—C10—N5	174.9 (2)
N4—Ni1—N6—C9	161.2 (2)	C9—N5—C10—C8	0.6 (3)
N3—Ni1—N6—C9	−32.1 (2)	O2—C6—O1—Ni1	170.75 (17)
N2—Ni1—N6—C8	−115.15 (19)	C5—C6—O1—Ni1	−9.9 (2)
O1—Ni1—N6—C8	53.55 (19)	N6—Ni1—O1—C6	−60.92 (15)
N4—Ni1—N6—C8	−23.60 (18)	N2—Ni1—O1—C6	56.8 (4)
N3—Ni1—N6—C8	143.16 (18)	N4—Ni1—O1—C6	26.84 (14)
C4—N1—C1—C2	146.7 (2)	N3—Ni1—O1—C6	−154.22 (15)
Ni1—N1—C1—C2	28.0 (2)	N1—Ni1—O1—C6	123.76 (15)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1C···O2^i	0.91	2.08	2.968 (3)	165
N2—H2C···I1^ii	0.90	3.02	3.843 (3)	153
N2—H2D···I1^iii	0.90	3.06	3.882 (2)	152
N3—H3C···I1^iv	0.90	3.15	3.894 (2)	141
N4—H4C···O2^i	0.90	2.37	3.184 (3)	151
N4—H4D···I1^iii	0.90	2.87	3.767 (2)	176
N5—H5B···O2^v	0.86	2.36	2.899 (3)	121
N5—H5B···I1^vi	0.86	3.26	3.882 (2)	132
O1W—HW1···O1^vii	0.90	1.84	2.733 (3)	174
O1W—HW2···I1^vi	0.91	2.65	3.537 (2)	164

Symmetry codes: (i) −x+2, −y+2, −z+2; (ii) −x+1, −y+1, −z+1; (iii) x, y+1, z; (iv) −x+3/2, y+1/2, −z+3/2; (v) x−1/2, −y+3/2, z−1/2; (vi) −x+1/2, y+1/2, −z+3/2; (vii) x−1, y, z.